Untargeted and Targeted Discrimination of Honey Collected by Apis cerana and Apis mellifera Based on Volatiles Using HS-GC-IMS and HS-SPME-GC–MS

Fraudulent acts regarding honey authenticity that use Apis mellifera honey as a substitute for Apis cerana honey have garnered considerable concern in China and triggered a trust crisis from consumers. In this study, untargeted metabolomics analysis was carried out based on volatile fractions in honey from A. cerana and A. mellifera using headspace gas chromatography–ion mobility spectrometry (HS-GC-IMS). Honey from A. cerana and A. mellifera was discriminated by HS-GC-IMS profiling, principal component analysis, and orthogonal partial least-squares discrimination analysis. Tentative markers were identified from p-values and the variable importance in projection analysis and confirmed using the retention index, mass fragments, and reference standards by gas chromatography–mass spectrometry (GC–MS). A targeted method was established using the headspace solid phase coupled with microextraction GC–MS (HS-SPME-GC–MS) to quantitate the markers. The results demonstrated that the developed untargeted and targeted metabolomics approach performed well when discriminating honey from A. cerana and A. mellifera.